JP5090907B2 - Silicon dioxide dispersion containing polyol - Google Patents
Silicon dioxide dispersion containing polyol Download PDFInfo
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- JP5090907B2 JP5090907B2 JP2007518491A JP2007518491A JP5090907B2 JP 5090907 B2 JP5090907 B2 JP 5090907B2 JP 2007518491 A JP2007518491 A JP 2007518491A JP 2007518491 A JP2007518491 A JP 2007518491A JP 5090907 B2 JP5090907 B2 JP 5090907B2
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- B32B17/069—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of intumescent material
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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Description
本発明は、ポリオールを含有する高フィラー含量の安定な二酸化ケイ素分散液並びにその製造方法及び使用に関する。 The present invention relates to a high filler content stable silicon dioxide dispersion containing a polyol and a process for its production and use.
高フィラー含量の二酸化ケイ素分散液を、断熱材、特に断熱ガラスのために使用することは知られている。 It is known to use high filler content silicon dioxide dispersions for insulation, in particular for insulation glass.
ＤＥ−Ａ−１９９４３１０３号は、８０質量％より高い含量の非晶質二酸化ケイ素を有する分散液を記載している。この関連において、非晶質とは、非常に低い表面積、有利には０．００１〜０．５ｍ2／ｇのＢＥＴ表面積を有する二酸化ケイ素を意味すると解釈されるべきである。非常に流し込みが容易であると記載されているが、特許請求の範囲に記載される分散液は、２時間以下といった短時間だけしか前記特性を保持しない。このことは、かかる分散液を、その製造直後に加工せねばならないことを意味し、つまりは貯蔵も輸送もできないことを意味する。 DE-A-19943103 describes a dispersion having an amorphous silicon dioxide content higher than 80% by weight. In this context, amorphous should be taken to mean silicon dioxide having a very low surface area, preferably a BET surface area of 0.001 to 0.5 m 2 / g. Although described as being very easy to pour, the dispersions described in the claims retain the properties only for a short time, such as 2 hours or less. This means that such a dispersion must be processed immediately after its production, that is, it cannot be stored or transported.
ＤＥ−Ａ−１９７２０２６９号は、ナノスケールの粒子、例えば二酸化ケイ素の含量少なくとも３５質量％を有する分散液を記載している。更にこの分散液は、１〜４０質量％の水又は有機溶剤を含有し、更に少なくとも２個の官能基を有する化合物、有利にはポリオール１０〜６０質量％より多くを含有する。また、この分散液は非常に低い安定性を有するにすぎず、迅速に加工せねばならない。より高エネルギーでの分散条件でさえも、前記挙動に何ら変化がもたらされないことが分かっている。 DE-A-19720269 describes a dispersion having a content of nanoscale particles, for example silicon dioxide, of at least 35% by weight. Furthermore, the dispersion contains 1 to 40% by weight of water or an organic solvent, and further contains a compound having at least two functional groups, preferably more than 10 to 60% by weight of polyol. Also, this dispersion has only a very low stability and must be processed quickly. It has been found that even the higher energy dispersion conditions do not change the behavior.
本発明の課題は、二酸化ケイ素を含有する高フィラー含量の分散液であって、比較的長時間にわたり安定であり、かつ低粘度を有する分散液を提供することである。特に、断熱ガラスの製造における先行技術分野による分散液よりも利点を示すことが望ましい。 An object of the present invention is to provide a dispersion having a high filler content containing silicon dioxide, which is stable for a relatively long time and has a low viscosity. In particular, it is desirable to show advantages over prior art dispersions in the production of insulating glass.
本発明は、安定な流し込み可能な二酸化ケイ素分散液であって、
− 分散液中の二酸化ケイ素粒子の数平均アグリゲート直径が、２００ｎｍ未満であり、かつ該分散液が、
− 少なくとも３５質量％の二酸化ケイ素粉末、
− ３〜３５質量％の少なくとも１種のポリオール、
− ２０〜６０質量％の水、
− ０〜１０質量％の添加剤、
（それぞれの場合において、分散液の全量に対するものである）
を含有し、かつ
− 該分散液は、アルカリ作用を有する物質を、１０＜ｐＨ≦１２のｐＨが確立される量で含有する
分散液を提供する。
The present invention is a stable pourable silicon dioxide dispersion comprising:
The number average aggregate diameter of the silicon dioxide particles in the dispersion is less than 200 nm, and the dispersion
At least 35% by weight of silicon dioxide powder,
-3 to 35% by weight of at least one polyol,
-20-60% by weight of water,
-0-10% by weight of additives,
(In each case, relative to the total amount of dispersion)
And-the dispersion provides a dispersion containing an alkaline substance in an amount such that a pH of 10 <pH ≦ 12 is established.
本発明の関連で、ここで、安定とは、二酸化ケイ素分散液が、少なくとも１ヶ月、一般に少なくとも３ヶ月の期間以内に顕著な沈殿を示さないことを意味すると解釈されるべきである。つまり、該分散液は、更なる濾過工程を行わずに該期間にわたり使用できる。更に、この期間のなかで、粘度の上昇は観察されないか、又は最低限の上昇しか観察されないべきである。これは、前記の期間のなかで、二酸化ケイ素分散液が、室温で流し込み可能であるというその特性を保つことを意味する。 In the context of the present invention, here stable should be taken to mean that the silicon dioxide dispersion does not show significant precipitation within a period of at least 1 month, generally at least 3 months. That is, the dispersion can be used over the period without further filtration steps. Furthermore, during this period, no increase in viscosity should be observed or only a minimal increase should be observed. This means that the silicon dioxide dispersion retains its characteristic of being able to be poured at room temperature during the above period.
本発明による二酸化ケイ素分散液は、添加剤を殺生剤又は分散助剤の形で含有してよい。しかしながら、多くの用途のために、これらの添加剤は、難点があると分かっていることもあり、本発明による分散液がかかる添加剤を含有しないことが好ましいこともある。 The silicon dioxide dispersion according to the invention may contain additives in the form of biocides or dispersion aids. However, for many applications, these additives may prove to be difficult and it may be preferred that the dispersion according to the invention does not contain such additives.
使用される二酸化ケイ素粉末の起源は、決定的ではない。このように例えば、沈降によって製造された二酸化ケイ素粉末又は熱分解法によって製造された二酸化ケイ素粉末が、該分散液中に存在してもよい。しかしながら、熱分解法で製造された金属酸化物粉末を有利に使用できることが判明した。 The origin of the silicon dioxide powder used is not critical. Thus, for example, silicon dioxide powder produced by sedimentation or silicon dioxide powder produced by pyrolysis may be present in the dispersion. However, it has been found that metal oxide powders produced by pyrolysis can be used advantageously.
熱分解法で製造された金属酸化物粉末は、一般に、金属酸化物前駆物質から、火炎加水分解又は火炎酸化によって酸水素炎中で得られる粉末を意味すると解釈される。前記方法で、ほぼ球状の一次粒子が最初に形成され、これらはともに焼結されて反応の間にアグリゲートとなる。次いで、該アグリゲートは、蓄積して、アグロメレートとなることもある。アグロメレートは、それが一般に比較的容易にエネルギーの導入によってアグリゲートに分離できるのに対して、アグリゲートの更なる破壊は、行うのであれば激しいエネルギーの導入によってのみ成される。 Metal oxide powders produced by pyrolysis are generally taken to mean powders obtained from metal oxide precursors in an oxyhydrogen flame by flame hydrolysis or flame oxidation. In the process, approximately spherical primary particles are first formed, which are sintered together to become an aggregate during the reaction. The aggregate may then accumulate and become an agglomerate. Agglomerates are generally relatively easily separable into aggregates by the introduction of energy, whereas further destruction of the aggregates can only be achieved by vigorous introduction of energy if it is done.
二酸化ケイ素は、一般に、四塩化ケイ素の火炎加水分解によって製造される。熱分解法の場合に、ケイ素−金属混合酸化物又は金属酸化物でドープされた二酸化ケイ素は、火炎加水分解又は火炎酸化を組み合わせることによって得ることもできる。熱分解法で製造された二酸化ケイ素粉末の他に、本発明による二酸化ケイ素分散液は、有利にはまた、カリウムドープされた二酸化ケイ素粉末を含有してよく、その製造方法は、例えばＤＥ−Ａ−１００６５０２８号に記載されている。 Silicon dioxide is generally produced by flame hydrolysis of silicon tetrachloride. In the case of pyrolysis processes, silicon dioxide doped with silicon-metal mixed oxides or metal oxides can also be obtained by a combination of flame hydrolysis or flame oxidation. In addition to the silicon dioxide powder produced by pyrolysis, the silicon dioxide dispersion according to the invention may also advantageously contain potassium-doped silicon dioxide powder, the process for example comprising DE-A -10065028.
熱分解法で製造された二酸化ケイ素粉末は、有利には５〜５００ｍ2／ｇ、特に有利には３０〜６０ｍ2／ｇの比表面積を有する。 The silicon dioxide powder produced by the pyrolysis method has a specific surface area of preferably 5 to 500 m 2 / g, particularly preferably 30 to 60 m 2 / g.
ポリオールの選択は、それが水との混和性を保持するのであれば、制限はない。好適なポリオールは、グリセロール、エチレングリコール、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ポリビニルアルコール、ポリエチレングリコール又はそれらの混合物であってよい。グリセロールが、この関連では特に好ましい。 The choice of polyol is not limited as long as it retains miscibility with water. Suitable polyols may be glycerol, ethylene glycol, trimethylolpropane, pentaerythritol, sorbitol, polyvinyl alcohol, polyethylene glycol or mixtures thereof. Glycerol is particularly preferred in this context.
同様にアルカリ作用を有する物質の選択は、それが水とポリオールとの液相中に可溶性であれば、制限はない。アルカリ金属水酸化物、アミン、（アルキル）アンモニウム水酸化物及び／又はアミノアルコールが好ましいことが判明した。水酸化カリウムは、特に好ましい。 Similarly, the selection of a substance having an alkaline action is not limited as long as it is soluble in the liquid phase of water and polyol. Alkali metal hydroxides, amines, (alkyl) ammonium hydroxides and / or amino alcohols have been found to be preferred. Potassium hydroxide is particularly preferred.
本発明による特に好ましい二酸化ケイ素分散液は、
− ３８〜６０質量％の熱分解法で製造された、ＢＥＴ表面積３０〜６０ｍ2／ｇを有する二酸化ケイ素粉末と、
− ５〜２５質量％のグリセロールと、
− ２５〜５０質量％の水と、
− ０．３〜０．７質量％のＫＯＨと
を含有する分散液であってよい。
Particularly preferred silicon dioxide dispersions according to the invention are
A silicon dioxide powder having a BET surface area of 30 to 60 m 2 / g, produced by a pyrolysis method of 38 to 60% by weight;
-5-25% by weight of glycerol,
-25-50% by weight of water;
-It may be a dispersion containing 0.3-0.7 wt% KOH.
出発物質及び分散液の製造の間に形成された物質の任意の不純物は、この中に含まれる。特に、熱分解法で製造された二酸化ケイ素粉末の分散液は、製造の結果として、付着した塩酸残分のため、酸性のｐＨを有する。これらの塩酸残分は、分散液中に存在するＫＯＨによって塩化カリウムへと中和される。 Any impurities of the starting material and material formed during the manufacture of the dispersion are included therein. In particular, the dispersion of silicon dioxide powder produced by the pyrolysis method has an acidic pH due to the residual hydrochloric acid residue as a result of the production. These hydrochloric acid residues are neutralized to potassium chloride by KOH present in the dispersion.
また本発明は、本発明による二酸化ケイ素分散液の製造方法において、
− 貯槽から、水と少なくとも１種のポリオールと場合により添加剤とを、ローター／ステーター式の装置を介して、後に望まれる組成に相当する量で循環させ、かつ
− 分散液のために望まれる二酸化ケイ素粉末の量を、充填装置を介して、連続的又は断続的に、かつローター／ステーター式の装置を作動させて、ローター歯のスリットとステータースリットとの間の剪断領域中に導入し、その際、ｐＨ値は、５未満であり、場合によりｐＨを酸の計量供給によって調整し、
− 充填装置を閉鎖し、更に分散を、ローター／ステーター式の装置の流量取り込み（ｃｕｒｒｅｎｔ ｕｐｔａｋｅ）がほとんど一定になるまで実施し、かつ
− アルカリ作用を有する物質の、分散液のｐＨを１０＜ｐＨ≦１２とする量を次いで添加し、その際、そのアルカリ作用を有する物質は、ゲル形成が起こらないほど迅速に添加する
製造方法を提供する。
The present invention also provides a method for producing a silicon dioxide dispersion according to the present invention,
-Circulating water, at least one polyol and optionally additives from the reservoir through a rotor / stator-type device in an amount corresponding to the composition desired later; and-desired for the dispersion An amount of silicon dioxide powder is introduced into the shear region between the rotor tooth slit and the stator slit by operating the rotor / stator type device continuously or intermittently through the filling device; At that time, the pH value is less than 5, and in some cases the pH is adjusted by metering acid,
The filling device is closed and further dispersion is carried out until the current uptake of the rotor / stator device is almost constant, and the pH of the dispersion of the substance with alkaline action is 10 <pH An amount of ≦ 12 is then added, in which case the substance having an alkaline action provides a production method which is added so rapidly that gel formation does not occur.
更に、本発明による二酸化ケイ素分散液は、
− 水と少なくとも１種のポリオールと場合により添加剤と二酸化ケイ素粉末との混合物を、まず後に望まれる組成に相当する量で、分散容器中に導入し、
− 分散を、遊星型混練機を用いることによって、７未満のｐＨで実施し、かつ
− 次いで、アルカリ作用を有する物質を、分散液のｐＨを１０＜ｐＨ≦１２とする量で添加する
方法によって得ることができる。
Furthermore, the silicon dioxide dispersion according to the invention is
Introducing a mixture of water, at least one polyol and optionally additives and silicon dioxide powder into the dispersion vessel first in an amount corresponding to the desired composition;
The dispersion is carried out at a pH of less than 7 by using a planetary kneader, and then the substance having an alkaline action is added in an amount such that the pH of the dispersion is 10 <pH ≦ 12. Can be obtained.
両方の方法において、分散液を過度に希釈しないために、アルカリ作用を有する物質としてできる限り高い濃度を有する水溶液を使用することが好ましい。アルカリ作用を有する物質を、２０〜５０質量％の濃度で使用することが好ましく、その際、水酸化カリウム溶液が特に好ましい。 In both methods, it is preferable to use an aqueous solution having the highest possible concentration as the substance having an alkaline action, in order not to dilute the dispersion excessively. A substance having an alkaline action is preferably used at a concentration of 20 to 50% by weight, and in this case, a potassium hydroxide solution is particularly preferred.
また、それらの方法は、ポリオールの添加を、二酸化ケイ素粉末の分散の後のみで、アルカリ作用を有する物質の添加の前に実施する手順によって実施することもできる。 These methods can also be carried out by a procedure in which the polyol is added only after the dispersion of the silicon dioxide powder and before the addition of the substance having an alkaline action.
本発明による分散液は、更に、前記のようにローター／ステーター式の装置又は遊星型混練機を用いて製造された分散液の少なくとも２つの部分流を、３５００ｋｇ／ｃｍ2までの圧力下に置き、かつノズルを介して開放し、そしてそれらの部分流を互いに合流させる手順によって得ることができる。 The dispersion according to the invention further comprises placing at least two partial streams of the dispersion produced using a rotor / stator type device or planetary kneader as described above under a pressure of up to 3500 kg / cm 2. and release to open via the nozzle, and their partial flow can be obtained by a procedure for combining with each other.
また本発明は、本発明による二酸化ケイ素分散液を、構造構成材間の、特に断熱ガラス配列の間の中空部の防炎性充填の構成材として用いる使用を提供する。 The invention also provides the use of the silicon dioxide dispersion according to the invention as a component for the flameproof filling of the hollows between the structural components, in particular between the insulating glass arrays.
更にまた、本発明による二酸化ケイ素分散液は、プラスチック、金属、木材、石膏ボード、フェルマセル（Ｆｅｒｍａｃｅｌ）、プレスボード、セラミック及び天然石又は人工石の構造構成材間の中空部の充填の部品並びに電線として、防炎目的のために使用することもできる。 Furthermore, the silicon dioxide dispersion according to the invention can be used as a part for filling hollow parts between plastic, metal, wood, gypsum board, Fermacel, press board, ceramic and structural components of natural stone or artificial stone and electric wires. It can also be used for flameproofing purposes.
また、該分散液は、構造構成材用の被覆組成物として使用でき、かつ熱安定性フォーム及び機械的安定性フォームを、例えばばら荷（Ｂｕｌｋ ｇｏｏｄｓ）又は成形体の形で製造するために適している。 The dispersion can also be used as a coating composition for structural components and is suitable for producing heat-stable foams and mechanically stable foams, for example in the form of bulk goods or molded bodies. ing.
本発明による分散液は、また、顔料又は（有機もしくは無機の、例えば繊維質、粉末状又は層状の）粗粒の非ナノスケールの添加剤、例えばマイカ顔料、酸化鉄、木粉、ガラス繊維、金属繊維、炭素繊維、砂、土及びベントナイトとの混合物中で、それにより製造できる材料の透明性が重要でなければ使用することができる。 The dispersions according to the invention can also contain pigments or coarse (non-nanoscale, organic or inorganic, eg fibrous, powdered or layered) additives such as mica pigments, iron oxide, wood flour, glass fibers, In mixtures with metal fibres, carbon fibres, sand, earth and bentonite, it can be used if the transparency of the material which can be produced is not important.
実施例：
実施例１：４２．５ｋｇの完全脱塩水及び２．２５ｋｇのグリセロールを、まず高級鋼製の混合容器中に導入する。６０ｋｇのＡＥＲＯＳＩＬ（登録商標）ＯＸ５０を、次いで、剪断条件下で、ローター／ステーター式の装置（Ｙｓｔｒａｌ Ｃｏｎｔｉ−ＴＤＳ３、ステータースリット：４ｍｍリング及び１ｍｍリング、ローター／ステーター間隔 約１ｍｍ、回転速度３０００ｒｐｍ）の吸込管を用いて吸引する。前記手順の間に、ｐＨが３．７に低下する。次いで、９ｋｇの水と、３．７５ｋｇのグリセロールと、同じ分散条件下で迅速に、３０質量％濃度の水酸化カリウム溶液２．０２ｋｇとを、連続的に添加する。
Example:
Example 1 : 42.5 kg of completely demineralized water and 2.25 kg of glycerol are first introduced into a mixing vessel made of high-grade steel. 60 kg of AEROSIL® OX50, then under shearing conditions of a rotor / stator type device (Ystral Conti-TDS3, stator slit: 4 mm ring and 1 mm ring, rotor / stator spacing approx. 1 mm, rotation speed 3000 rpm) Aspirate with suction tube. During the procedure, the pH drops to 3.7. 9 kg of water, 3.75 kg of glycerol and 2.02 kg of 30% strength by weight potassium hydroxide solution are then added continuously under the same dispersion conditions.
実施例２〜９を、同様に実施し、かつ実施例１０においては、水酸化カリウム溶液を添加しない。分散液の製造のために使用した量は、第１表に見ることができる。 Examples 2 to 9 are carried out in the same way and in example 10 no potassium hydroxide solution is added. The amounts used for the preparation of the dispersion can be found in Table 1.
分散液の組成及びその物理化学的値を、第２表に示す。実施例３ａは、実施例３の分散液を、引き続き高エネルギーミルで２５００バール下で粉砕したものの値を示す。 The composition of the dispersion and its physicochemical values are shown in Table 2. Example 3a shows the value of the dispersion of Example 3 which was subsequently ground in a high energy mill under 2500 bar.
実施例１〜８は、本発明による分散液であり、実施例９及び１０は、比較例である。 Examples 1 to 8 are dispersions according to the present invention, and Examples 9 and 10 are comparative examples.
実施例１１において、二酸化ケイ素分散液をまず、より高い二酸化ケイ素濃度で分散させ、そして所望の濃度に希釈してから、水酸化カリウムを添加する。 In Example 11, the silicon dioxide dispersion is first dispersed at a higher silicon dioxide concentration and diluted to the desired concentration before adding potassium hydroxide.
実施例１１：
３６．１ｋｇの完全脱塩水及び９．０ｋｇのグリセロールを、まず高級鋼製の混合容器中に導入する。６０ｋｇのＡＥＲＯＳＩＬ（登録商標）ＯＸ５０を、次いで、剪断条件下で、ローター／ステーター式の装置（Ｙｓｔｒａｌ Ｃｏｎｔｉ−ＴＤＳ３、ステータースリット：４ｍｍリング及び１ｍｍリング、ローター／ステーター間隔 約１ｍｍ／回転速度３０００ｒｐｍ）の吸込管を用いて吸引し、１５分間剪断する。ＳｉＯ2濃度は、５７質量％である。そのｐＨは、前記手順の間に、"酸性の"ＡＥＲＯＳＩＬ（登録商標）によって３．５に低下する。次いで、１５．２ｋｇのグリセロールを添加し、そして数分間均質化させた後に、１０．９のｐＨを、２．２ｋｇの３０質量％濃度の水酸化カリウム溶液によって、同じ分散条件下で迅速に確立させる。最後に、更に１．０ｋｇの水を添加して、ＳｉＯ2濃度４８．６及びグリセロール濃度１９．６を確立する。ｐＨは、前記の少量の水によってほんの僅かしか変化しない。
Example 11 :
36.1 kg of completely demineralized water and 9.0 kg of glycerol are first introduced into a high-grade steel mixing vessel. 60 kg of AEROSIL® OX50, then under shearing conditions of a rotor / stator type device (Ystral Conti-TDS3, stator slit: 4 mm ring and 1 mm ring, rotor / stator spacing approx. 1 mm / rotation speed 3000 rpm) Suction with suction tube and shear for 15 minutes. The SiO 2 concentration is 57% by mass. The pH is lowered to 3.5 by “acidic” AEROSIL® during the procedure. Then, after adding 15.2 kg of glycerol and homogenizing for a few minutes, a pH of 10.9 is rapidly established under the same dispersion conditions with 2.2 kg of 30% strength by weight potassium hydroxide solution Let Finally, an additional 1.0 kg of water is added to establish a SiO 2 concentration of 48.6 and a glycerol concentration of 19.6. The pH changes only slightly with the small amount of water.
実施例１〜８及び１１の本発明による分散液は、全てが非常に低い粘度を有する。該分散液中の二酸化ケイ素粒子の平均アグリゲート直径（数平均）は、１５０ｎｍ未満である。 The inventive dispersions of Examples 1-8 and 11 all have very low viscosities. The average aggregate diameter (number average) of the silicon dioxide particles in the dispersion is less than 150 nm.
実施例１１で、高い二酸化ケイ素濃度で分散させ、引き続き所望の濃度に希釈することによって得られた分散液は、分散を所望の濃度で直接実施した方法より利点を示している。粉砕は、より強力であり、かつ分散液の粘度は、より低い。 In Example 11, the dispersion obtained by dispersing at a high silicon dioxide concentration and subsequently diluting to the desired concentration shows advantages over the method in which the dispersion was carried out directly at the desired concentration. Milling is more powerful and the viscosity of the dispersion is lower.
本発明による実施例３ａによる、高エネルギー粉砕によって製造された分散液は、更に粘度と粒度の低下を示す。 The dispersion produced by high energy grinding according to Example 3a according to the invention further exhibits a reduction in viscosity and particle size.
実施例７ａは、気候制御されたチャンバ中で３ヶ月間貯蔵した後の分散液７の値を示している。ここでは、その温度を、一日で１０℃と５０℃との間で変動させる。３ヶ月後でさえも、本発明による二酸化ケイ素分散液は、なおも優れた粘度値を示している。 Example 7a shows the value of dispersion 7 after storage for 3 months in a climate controlled chamber. Here, the temperature is varied between 10 ° C. and 50 ° C. in one day. Even after 3 months, the silicon dioxide dispersion according to the invention still exhibits excellent viscosity values.
ｐＨ１１．８を有する分散液８は、非常に低い粘度を示す。更なるｐＨの増大は、まさに、更なる粘度の低下をまねくが、二酸化ケイ素粒子の初期溶解を既に観察することができる。ケイ酸カリウムは、温度と時間とに依存して、二酸化ケイ素の初期溶解のため、ますます形成される。反応が進むにつれ、増大するＳｉＯ2／Ｋ2Ｏ比によってカリウム水ガラスは、均一相としての希釈された低粘度水酸化カリウム溶液からますます形成される。水酸化カリウム溶液は、前記反応で消費されるので、ＫＯＨを、高いｐＨの保持のために再び添加する必要があるが、この結果として、カリウム水ガラス反応も再び促進される。しかしながら、カリウム水ガラスは、ＳｉＯ2／Ｋ2Ｏ比と濃度とが増大するので、粘度の顕著な増大を示す。かかる時間−及び温度依存性反応を抑制するために、１２未満のｐＨが必須である。 Dispersion 8 having a pH of 11.8 exhibits a very low viscosity. A further increase in pH just leads to a further decrease in viscosity, but an initial dissolution of the silicon dioxide particles can already be observed. Potassium silicate is increasingly formed due to the initial dissolution of silicon dioxide, depending on temperature and time. As the reaction proceeds, potassium water glass is increasingly formed from diluted low viscosity potassium hydroxide solution as a homogeneous phase due to the increasing SiO 2 / K 2 O ratio. Since potassium hydroxide solution is consumed in the reaction, it is necessary to add KOH again to maintain a high pH, and as a result, the potassium water glass reaction is promoted again. However, potassium water glass shows a significant increase in viscosity as the SiO 2 / K 2 O ratio and concentration increase. In order to suppress such time- and temperature-dependent reactions, a pH of less than 12 is essential.
１０未満のアルカリ性のｐＨ値では、粘度の大きな増大が同様に観察することができる（実施例９）。ＫＯＨを添加しなかった分散液は、相当より高い粘度を示し、数日でゲル化する（実施例１０）。 At alkaline pH values below 10, a large increase in viscosity can be observed as well (Example 9). The dispersion without the addition of KOH exhibits a considerably higher viscosity and gels in a few days (Example 10).
驚くべきことに、本発明によるポリオール含有の二酸化ケイ素分散液は、１０より高いｐＨでのみ低い粘度を有する。ポリオールを含有しない純粋に水性の分散液においては、粘度低下は、既に約９のｐＨで開始することが知られている。 Surprisingly, the polyol-containing silicon dioxide dispersion according to the invention has a low viscosity only at a pH higher than 10. In purely aqueous dispersions containing no polyol, it is known that the viscosity reduction already starts at a pH of about 9.
本発明による二酸化ケイ素分散液の製造において、二酸化ケイ素粉末をまず５又はそれ未満の酸性範囲のｐＨで分散させ、そしてアルカリ作用を有する物質を、同じ分散条件下で迅速に添加することが必須である。アルカリ作用を有する物質をゆっくりと添加した場合には、迅速なゲル形成が起こる。 In the production of the silicon dioxide dispersion according to the invention, it is essential that the silicon dioxide powder is first dispersed at a pH in the acidic range of 5 or less and the alkaline substance is rapidly added under the same dispersion conditions. is there. When a substance having an alkaline action is added slowly, rapid gel formation occurs.
Claims (13)
− 分散液中の二酸化ケイ素粒子の数平均アグリゲート直径が、２００ｎｍ未満であり、かつ該分散液が、
− 少なくとも３５質量％の二酸化ケイ素粉末、
− ３〜３５質量％の少なくとも１種のポリオール、
− ２０〜６０質量％の水、
− ０〜１０質量％の添加剤、
（それぞれの場合において、分散液の全量に対するものである）
を含有し、かつ
− 該分散液は、アルカリ作用を有する物質を、１０＜ｐＨ≦１２のｐＨが確立される量で含有する、
安定な流し込み可能な二酸化ケイ素分散液。A stable pourable silicon dioxide dispersion,
The number average aggregate diameter of the silicon dioxide particles in the dispersion is less than 200 nm, and the dispersion
At least 35% by weight of silicon dioxide powder,
-3 to 35% by weight of at least one polyol,
-20-60% by weight of water,
-0-10% by weight of additives,
(In each case, relative to the total amount of dispersion)
And the dispersion contains a substance having an alkaline action in an amount such that a pH of 10 <pH ≦ 12 is established ,
Silicon dioxide dispersion that can be poured stably.
− ３８〜６０質量％の熱分解法で製造された、ＢＥＴ表面積３０〜６０ｍ2／ｇを有する二酸化ケイ素粉末と、
− ５〜２５質量％のグリセロールと、
− ２５〜５０質量％の水と、
− ０．３〜０．７質量％のＫＯＨと
を含有する安定な流し込み可能な二酸化ケイ素分散液。The stable pourable silicon dioxide dispersion of claim 1, which is
A silicon dioxide powder having a BET surface area of 30 to 60 m 2 / g, produced by a pyrolysis method of 38 to 60% by weight;
-5-25% by weight of glycerol,
-25-50% by weight of water;
A stable pourable silicon dioxide dispersion containing 0.3 to 0.7% by weight of KOH.
− 貯槽から、水と少なくとも１種のポリオールと場合により添加剤とを、ローター／ステーター式の装置を介して、後に望まれる組成に相当する量で循環させ、かつ
− 分散液のために望まれる二酸化ケイ素粉末の量を、充填装置を介して、連続的又は断続的に、かつローター／ステーター式の装置を作動させて、ローター歯のスリットとステータースリットとの間の剪断領域中に導入し、その際、ｐＨ値は、５未満であり、場合によりｐＨを酸の計量供給によって調整し、
− 充填装置を閉鎖し、更に分散を、ローター／ステーター式の装置の流量取り込みがほとんど一定になるまで実施し、かつ
− アルカリ作用を有する物質の、分散液のｐＨを１０＜ｐＨ≦１２とする量を次いで添加し、その際、そのアルカリ作用を有する物質は、ゲル形成が起こらないほど迅速に添加する
ことを特徴とする製造方法。In the manufacturing method of the silicon dioxide dispersion of any one of Claim 1-7,
-Circulating water, at least one polyol and optionally additives from the reservoir through a rotor / stator-type device in an amount corresponding to the composition desired later; and-desired for the dispersion An amount of silicon dioxide powder is introduced into the shear region between the rotor tooth slit and the stator slit by operating the rotor / stator type device continuously or intermittently through the filling device; At that time, the pH value is less than 5, and in some cases the pH is adjusted by metering acid,
-The filling device is closed and further dispersion is carried out until the flow rate uptake of the rotor / stator device is almost constant, and-the pH of the dispersion of the substance with alkaline action is 10 <pH≤12 An amount is then added, wherein the substance having an alkaline action is added so rapidly that gel formation does not occur.
− 水と少なくとも１種のポリオールと場合により添加剤と二酸化ケイ素粉末との混合物を、まず後に望まれる組成に相当する量で、分散容器中に導入し、
− 分散を、遊星型混練機を用いることによって、７未満のｐＨで実施し、かつ
− 次いで、アルカリ作用を有する物質を、分散液のｐＨを１０〜１２とする量で添加する
ことを特徴とする製造方法。In the manufacturing method of the silicon dioxide dispersion of any one of Claim 1-7,
Introducing a mixture of water, at least one polyol and optionally additives and silicon dioxide powder into the dispersion vessel first in an amount corresponding to the desired composition;
-Dispersion is carried out at a pH of less than 7 by using a planetary kneader; and-a substance having an alkaline action is then added in an amount such that the pH of the dispersion is 10-12. Manufacturing method.
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| DE102004031785A DE102004031785A1 (en) | 2004-07-01 | 2004-07-01 | Polyol-containing silica dispersion |
| DE102004031785.2 | 2004-07-01 | ||
| PCT/EP2005/006481 WO2006002773A1 (en) | 2004-07-01 | 2005-06-16 | Silicon dioxide dispersion comprising polyol |
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Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004031785A1 (en) * | 2004-07-01 | 2006-01-26 | Degussa Ag | Polyol-containing silica dispersion |
| DE102004037045A1 (en) | 2004-07-29 | 2006-04-27 | Degussa Ag | Aqueous silane nanocomposites |
| DE102004037044A1 (en) | 2004-07-29 | 2006-03-23 | Degussa Ag | Agent for equipping cellulose-based and / or starch-based substrates with water-repellent and, at the same time, fungus, bacteria, insect and algae-deficient properties |
| DE102004049427A1 (en) | 2004-10-08 | 2006-04-13 | Degussa Ag | Polyether-functional siloxanes, polyethersiloxane-containing compositions, processes for their preparation and their use |
| DE102005004872A1 (en) | 2005-02-03 | 2006-08-10 | Degussa Ag | Aqueous emulsions of functional alkoxysilanes and their condensed oligomers, their preparation and use for surface treatment |
| DE102005032427A1 (en) * | 2005-07-12 | 2007-01-18 | Degussa Ag | Aluminum oxide dispersion |
| GB0514753D0 (en) * | 2005-07-19 | 2005-08-24 | Pilkington Plc | Fire resistant glazings |
| DE102006006655A1 (en) * | 2005-08-26 | 2007-03-01 | Degussa Ag | Cellulose- or lignocellulose-containing composites based on a silane-based composite as binder |
| DE102006006656A1 (en) | 2005-08-26 | 2007-03-01 | Degussa Ag | Silane-containing binder for composites |
| DE102005053071A1 (en) * | 2005-11-04 | 2007-05-16 | Degussa | Process for the preparation of ultrafine powders based on polymaiden, ultrafine polyamide powder and their use |
| DE102006003956A1 (en) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Production of a corrosion protection layer on a metal surface e.g. vehicle structure comprises applying a sol-gel composition to the metal surface, drying and/or hardening and applying a further layer and drying and/or hardening |
| DE102006013090A1 (en) * | 2006-03-20 | 2007-09-27 | Georg-August-Universität Göttingen | Composite material made of wood and thermoplastic material |
| DE102006017701A1 (en) * | 2006-04-15 | 2007-10-25 | Degussa Gmbh | Silicon-titanium mixed oxide powder, dispersion thereof and titanium-containing zeolite produced therefrom |
| PL2029355T3 (en) * | 2006-06-15 | 2017-09-29 | Agc Glass Europe | Fire-protective glazing |
| US8155674B2 (en) * | 2006-08-22 | 2012-04-10 | Research In Motion Limited | Apparatus, and associated method, for dynamically configuring a page message used to page an access terminal in a radio communication system |
| DE102006039269A1 (en) * | 2006-08-22 | 2008-02-28 | Evonik Degussa Gmbh | Dispersion of alumina, coating composition and ink receiving medium |
| DE102006049524A1 (en) * | 2006-10-20 | 2008-04-24 | Evonik Degussa Gmbh | Aqueous dispersions of precipitated silicas and silicates to increase the early strength in cementitious preparations |
| ES2725499T3 (en) * | 2007-04-20 | 2019-09-24 | Evonik Degussa Gmbh | Mixture containing an organosilicon compound and its use |
| EP1997622A1 (en) | 2007-05-25 | 2008-12-03 | AGC Flat Glass Europe SA | Fireproof glazing |
| JP2008308362A (en) * | 2007-06-14 | 2008-12-25 | Sumitomo Osaka Cement Co Ltd | Transparent inorganic oxide dispersion liquid, transparent composite material, and their producing methods |
| DE102007038314A1 (en) | 2007-08-14 | 2009-04-16 | Evonik Degussa Gmbh | Process for the controlled hydrolysis and condensation of epoxy-functional organosilanes and their condensation with further organofunctional alkoxysilanes |
| DE102007040246A1 (en) * | 2007-08-25 | 2009-02-26 | Evonik Degussa Gmbh | Radiation-curable formulations |
| DE102008007261A1 (en) | 2007-08-28 | 2009-03-05 | Evonik Degussa Gmbh | Aqueous silane systems based on bis (trialkoxysilylalkyl) amines |
| DE102007049743A1 (en) * | 2007-10-16 | 2009-04-23 | Evonik Degussa Gmbh | Silicon-titanium mixed oxide powder, dispersion thereof and titanium-containing zeolite produced therefrom |
| DE102007049742A1 (en) * | 2007-10-16 | 2009-04-23 | Evonik Degussa Gmbh | Process for the preparation of a dispersion containing titanium-silicon mixed oxide |
| EP2072247A1 (en) * | 2007-12-17 | 2009-06-24 | AGC Flat Glass Europe SA | Fireproof glazing |
| EP2111977A1 (en) * | 2008-04-25 | 2009-10-28 | AGC Flat Glass Europe SA | Fireproof glazing |
| EP2130673A1 (en) * | 2008-06-04 | 2009-12-09 | AGC Flat Glass Europe SA | Fireproof glazing |
| WO2009155714A1 (en) | 2008-06-26 | 2009-12-30 | Gevartis Ag | Materials for producing transparent heat protection elements and light protection elements produced using such materials and also processes for producing them |
| EP2145928B1 (en) * | 2008-07-18 | 2017-09-13 | Evonik Degussa GmbH | Dispersion made of hydrophobic silicon dioxide particles and granulate made from same |
| EP2199074A1 (en) | 2008-12-18 | 2010-06-23 | AGC Flat Glass Europe SA | Fireproof glazing |
| JP5167178B2 (en) * | 2009-03-18 | 2013-03-21 | 株式会社リコー | High gloss variable printing media and recording method |
| DE102009002499A1 (en) | 2009-04-20 | 2010-10-21 | Evonik Degussa Gmbh | Dispersion comprising surface-modified silica particles with quaternary, amino-functional organosilicon compounds |
| DE102009002477A1 (en) | 2009-04-20 | 2010-10-21 | Evonik Degussa Gmbh | Quaternary amino functional, organosilicon compounds containing composition and their preparation and use |
| BE1019901A3 (en) * | 2011-04-06 | 2013-02-05 | Agc Glass Europe | FIRE RESISTANT GLAZING. |
| EP2557141B1 (en) * | 2011-08-10 | 2015-04-08 | AMATO GmbH Brandschutzsysteme | Laminar fire prevention component, use of same and method for producing same |
| US10322975B2 (en) * | 2013-03-01 | 2019-06-18 | Kyoto University | Method for producing liquid dispersion of ceramic microparticles |
| DE202014006615U1 (en) * | 2013-11-29 | 2015-10-15 | Pilkington Group Limited | Fire resistant material |
| CN103922352A (en) * | 2014-03-30 | 2014-07-16 | 苏州奈微纳米科技有限公司 | Nano silicon dioxide dispersoid and preparation method thereof |
| CN104893363A (en) * | 2015-06-05 | 2015-09-09 | 确成硅化学股份有限公司 | Modification method of precipitation-process silica white |
| CN107922197B (en) | 2015-07-10 | 2021-11-19 | 赢创运营有限公司 | Metal oxide-containing dispersions having high salt stability |
| PL3319906T3 (en) | 2015-07-10 | 2022-01-31 | Evonik Operations Gmbh | Sio2 containing dispersion with high salt stability |
| EP3368633B1 (en) | 2015-10-26 | 2020-05-27 | Evonik Operations GmbH | Method of obtaining mineral oil using a silica fluid |
| US10577526B2 (en) * | 2017-09-11 | 2020-03-03 | Saudi Arabian Oil Company | Loss circulation material composition having an acidic nanoparticle based dispersion and polyamine |
| CN108479648A (en) * | 2018-04-28 | 2018-09-04 | 郭舒洋 | A kind of preparation method of stable type modified silicasol |
| EP3887309A1 (en) * | 2018-11-29 | 2021-10-06 | Evonik Operations GmbH | Aqueous silica dispersion with long shelf life for fire-resistant glass |
| CN113429983B (en) * | 2021-06-23 | 2022-05-10 | 应急管理部天津消防研究所 | A kind of high refractory transparent fireproof gel and preparation method thereof and composite fireproof glass |
| CN115820133A (en) * | 2022-12-23 | 2023-03-21 | 硅品(北京)新材料科技有限公司 | A silicic acid-based material with light-transmitting heat-insulating protective layer and a manufacturing method of the protective layer |
Family Cites Families (81)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2984629A (en) * | 1957-11-04 | 1961-05-16 | Cabot Corp | Aqueous dispersions of pyrogenic silica |
| US3004921A (en) * | 1958-06-11 | 1961-10-17 | Argus Chem | Preparation of colloidal dispersions of fine-particle size silica hydrogel in polyols |
| US3046234A (en) * | 1959-12-07 | 1962-07-24 | Monsanto Chemicals | Stable alkaline silica sols containing certain dialdehydes |
| US3655578A (en) * | 1969-05-08 | 1972-04-11 | Du Pont | High surface area stabilized silica sols and process for preparing same |
| US4430369A (en) * | 1982-06-01 | 1984-02-07 | Nalco Chemical Company | Silica sol penetration and saturation of thermal insulation fibers |
| US5246624A (en) * | 1989-03-21 | 1993-09-21 | Cabot Corporation | Aqueous colloidal dispersion of fumed silica, acid and stabilizer |
| CA2113845A1 (en) * | 1994-01-20 | 1995-07-21 | Edward J. Farkas | Control system for filling tanks with saturated liquids |
| DE19720269A1 (en) * | 1997-05-14 | 1998-11-19 | Inst Neue Mat Gemein Gmbh | Nanocomposite for thermal insulation purposes |
| EP1148026B1 (en) * | 2000-04-12 | 2016-08-10 | Evonik Degussa GmbH | Dispersions |
| DE50016060D1 (en) * | 2000-09-26 | 2011-03-03 | Evonik Degussa Gmbh | Iron oxide and silica-titanium dioxide mixture |
| DE10049153A1 (en) * | 2000-09-27 | 2002-04-11 | Degussa | Paint, varnish, pollutants, bioorganisms, oil, water, and / or dirt-repellent coating |
| DE10054345A1 (en) * | 2000-11-02 | 2002-05-08 | Degussa | Aqueous dispersion, process for its preparation and use |
| DE10065027A1 (en) * | 2000-12-23 | 2002-07-04 | Degussa | Aqueous dispersion, process for its preparation and use |
| DE10126163A1 (en) * | 2001-05-30 | 2002-12-05 | Degussa | Solid, semi-solid or liquid pharmaceutical or cosmetic preparations, containing pyrogenic silicon dioxide of high tamped density as auxiliary to provide good flow properties |
| EP1284277B1 (en) * | 2001-08-08 | 2004-10-20 | Degussa Aktiengesellschaft | Silica-coated metal oxide particles |
| DE10149130A1 (en) * | 2001-10-05 | 2003-04-10 | Degussa | Flame hydrolytic alumina doped with divalent metal oxide is used in aqueous dispersion for chemical-mechanical polishing of metallic and nonmetallic surfaces, coating paper or producing special glass |
| DE10152745A1 (en) * | 2001-10-25 | 2003-05-15 | Degussa | Alumina dispersion |
| US7815936B2 (en) * | 2001-10-30 | 2010-10-19 | Evonik Degussa Gmbh | Use of granular materials based on pyrogenically produced silicon dioxide in pharmaceutical compositions |
| US20030108580A1 (en) * | 2001-10-30 | 2003-06-12 | Steffen Hasenzahl | Use of granulates based on pyrogenically - produced silicon dioxide in cosmetic compositions |
| DE10163938A1 (en) * | 2001-12-22 | 2003-07-10 | Degussa | Flame-hydrolytically produced silicon-titanium mixed oxide powder with surface-enriched silicon dioxide, its production and use |
| DE10203047A1 (en) * | 2002-01-26 | 2003-08-07 | Degussa | Cationic mixed oxide dispersion, coating color and ink-absorbing medium |
| DE10204471C1 (en) * | 2002-02-05 | 2003-07-03 | Degussa | Aqueous dispersion of cerium oxide-coated doped silica powder, used for chemical-mechanical polishing of semiconductor substrate or coating or in shallow trench insulation, is obtained by mixing doped silica core with cerium salt solution |
| DE10204470C1 (en) * | 2002-02-05 | 2003-08-14 | Degussa | Production of finely divided stable dispersion of solids comprises injecting streams of pre-dispersion via high pressure pumps through nozzle into reactor chamber, introducing water vapor, and removing dispersion and vapor |
| DE10205280C1 (en) * | 2002-02-07 | 2003-07-03 | Degussa | Aqueous dispersion used for chemical-mechanical polishing of oxide surface, preferably silica, contains pyrogenic silica powder doped with alumina from aerosol with specified particle size |
| DE50300055D1 (en) * | 2002-03-22 | 2004-09-23 | Degussa | Dispersion, coating color and recording medium |
| DE10225125A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag Th | Aqueous dispersion containing pyrogenic titanium, zinc, iron or cerium oxide particles, useful for preparing cosmetic formulations, includes a phosphate ester or maleic copolymer dispersant |
| DE10225122A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag Th | Highly concentrated aqueous dispersions containing hydrophobic microfine metal oxide particles and dispersing agents |
| DE10225123A1 (en) * | 2002-06-06 | 2003-12-18 | Goldschmidt Ag Th | Highly concentrated aqueous dispersion containing hydrophilic microfine metal oxide particles and dispersing agents |
| DE10229761B4 (en) * | 2002-07-03 | 2004-08-05 | Degussa Ag | Aqueous dispersion containing pyrogenically produced metal oxide particles and phosphates, process for their preparation and their use |
| US7374787B2 (en) * | 2002-08-22 | 2008-05-20 | Dequssa Ag | Stabilized, aqueous silicon dioxide dispersion |
| DE10239144A1 (en) * | 2002-08-27 | 2004-03-18 | Degussa Ag | dispersion |
| DE60328407D1 (en) * | 2002-10-14 | 2009-08-27 | Akzo Nobel Nv | AQUEOUS SILICON DIOXIDE DISPERSION |
| DE10250711A1 (en) * | 2002-10-31 | 2004-05-19 | Degussa Ag | Pharmaceutical and cosmetic preparations |
| DE10250712A1 (en) * | 2002-10-31 | 2004-05-19 | Degussa Ag | Powdery substances |
| DE10256267A1 (en) * | 2002-12-03 | 2004-06-24 | Degussa Ag | Dispersion, coating color and recording medium |
| DE10259860A1 (en) * | 2002-12-20 | 2004-07-08 | Degussa Ag | Powder mixture consisting of titanium dioxide, zinc oxide and zinc-titanium mixed oxide |
| DE10260718A1 (en) * | 2002-12-23 | 2004-07-08 | Degussa Ag | Titanium dioxide coated with silicon dioxide |
| DE10316661A1 (en) * | 2003-04-11 | 2004-11-04 | Degussa Ag | Aqueous dispersion of hydrophobized silicon dioxide powder containing dispersants |
| DE10317066A1 (en) * | 2003-04-14 | 2004-11-11 | Degussa Ag | Process for the preparation of metal oxide and metalloid oxide dispersions |
| DE10330020A1 (en) * | 2003-07-03 | 2005-01-20 | Degussa Ag | Highly filled silane preparation |
| DE10337198A1 (en) * | 2003-08-13 | 2005-03-17 | Degussa Ag | Carriers based on granules produced from pyrogenically prepared silicon dioxides |
| DE10360087A1 (en) * | 2003-12-20 | 2005-07-21 | Degussa Ag | Flame hydrolysis produced, hochoberflächiges alumina powder |
| DE10360766A1 (en) * | 2003-12-23 | 2005-07-28 | Degussa Ag | Process and apparatus for the preparation of dispersions |
| DE102004004147A1 (en) * | 2004-01-28 | 2005-08-18 | Degussa Ag | Surface-modified silica-sheathed metalloid / metal oxides |
| DE102004021092A1 (en) * | 2004-04-29 | 2005-11-24 | Degussa Ag | Use of a cationic silica dispersion as a textile finishing agent |
| DE102004025143A1 (en) * | 2004-05-21 | 2005-12-08 | Degussa Ag | Ternary metal mixed oxide powder |
| DE102004025767A1 (en) * | 2004-05-26 | 2005-12-22 | Degussa Ag | Stable solutions of N-substituted aminopolysiloxanes, their preparation and use |
| DE102004031785A1 (en) * | 2004-07-01 | 2006-01-26 | Degussa Ag | Polyol-containing silica dispersion |
| DE102004037043A1 (en) * | 2004-07-29 | 2006-03-23 | Degussa Ag | Block condensates of organofunctional siloxanes, their preparation, use and their properties |
| DE102004037045A1 (en) * | 2004-07-29 | 2006-04-27 | Degussa Ag | Aqueous silane nanocomposites |
| DE102004037044A1 (en) * | 2004-07-29 | 2006-03-23 | Degussa Ag | Agent for equipping cellulose-based and / or starch-based substrates with water-repellent and, at the same time, fungus, bacteria, insect and algae-deficient properties |
| DE102004037118A1 (en) * | 2004-07-30 | 2006-03-23 | Degussa Ag | Titanium dioxide-containing dispersion |
| DE102004046093A1 (en) * | 2004-09-23 | 2006-03-30 | Degussa Ag | Surface-modified zinc-titanium mixed oxides |
| DE102004049427A1 (en) * | 2004-10-08 | 2006-04-13 | Degussa Ag | Polyether-functional siloxanes, polyethersiloxane-containing compositions, processes for their preparation and their use |
| DE102004053384A1 (en) * | 2004-11-02 | 2006-05-04 | Degussa Ag | Liquid, viscous agent based on an organofunctional silane system for the production of weather-resistant protective coatings to prevent contamination of surfaces |
| DE102004056862A1 (en) * | 2004-11-25 | 2006-06-14 | Degussa Ag | Powdered, high water content cosmetic preparation |
| EP1700825A1 (en) * | 2004-12-23 | 2006-09-13 | Degussa AG | Surface and structure modified titanium dioxide |
| ES2299790T3 (en) * | 2004-12-23 | 2008-06-01 | Evonik Degussa Gmbh | TITANIUM DIOXIDES PRODUCED BY VIA PIROGENA AND SUPERFICIALLY MODIFIED. |
| EP1674534B1 (en) * | 2004-12-23 | 2010-10-13 | Evonik Degussa GmbH | surface-modified silicon dioxide titanium dioxide mixed oxides |
| EP1674427A1 (en) * | 2004-12-23 | 2006-06-28 | Degussa AG | Structure modified titanium dioxides |
| DE102005055226A1 (en) * | 2004-12-24 | 2006-07-13 | Degussa Ag | Storage of powdery substances with a high water content |
| DE102005004871A1 (en) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Highly viscous aqueous emulsions of functional alkoxysilanes, their condensed oligomers, organopolysiloxanes, their preparation and their use for the surface treatment of inorganic materials |
| DE102005004872A1 (en) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Aqueous emulsions of functional alkoxysilanes and their condensed oligomers, their preparation and use for surface treatment |
| DE102005032427A1 (en) * | 2005-07-12 | 2007-01-18 | Degussa Ag | Aluminum oxide dispersion |
| DE102006006655A1 (en) * | 2005-08-26 | 2007-03-01 | Degussa Ag | Cellulose- or lignocellulose-containing composites based on a silane-based composite as binder |
| DE102006006656A1 (en) * | 2005-08-26 | 2007-03-01 | Degussa Ag | Silane-containing binder for composites |
| DE102006006654A1 (en) * | 2005-08-26 | 2007-03-01 | Degussa Ag | Composite materials based on wood or other plant materials, e.g. chipboard, fibreboard, plywood or plant pots, made by using special aminoalkyl-alkoxy-silane compounds or their cocondensates as binders |
| DE102005053071A1 (en) * | 2005-11-04 | 2007-05-16 | Degussa | Process for the preparation of ultrafine powders based on polymaiden, ultrafine polyamide powder and their use |
| DE102005059960A1 (en) * | 2005-12-15 | 2007-06-28 | Degussa Gmbh | Highly filled transition alumina-containing dispersion |
| DE102006003957A1 (en) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Water-dilutable sol-gel for coating paper, cardboard, wood, presspahn, plastics, lacquer, stone, ceramics, metal or alloy or as primer is obtained by reacting glycidyloxypropylalkoxysilane, aqueous silica sol, organic acid and crosslinker |
| DE102006003956A1 (en) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Production of a corrosion protection layer on a metal surface e.g. vehicle structure comprises applying a sol-gel composition to the metal surface, drying and/or hardening and applying a further layer and drying and/or hardening |
| DE102006013090A1 (en) * | 2006-03-20 | 2007-09-27 | Georg-August-Universität Göttingen | Composite material made of wood and thermoplastic material |
| DE102006017701A1 (en) * | 2006-04-15 | 2007-10-25 | Degussa Gmbh | Silicon-titanium mixed oxide powder, dispersion thereof and titanium-containing zeolite produced therefrom |
| DE102006039269A1 (en) * | 2006-08-22 | 2008-02-28 | Evonik Degussa Gmbh | Dispersion of alumina, coating composition and ink receiving medium |
| ES2725499T3 (en) * | 2007-04-20 | 2019-09-24 | Evonik Degussa Gmbh | Mixture containing an organosilicon compound and its use |
| DE102007038314A1 (en) * | 2007-08-14 | 2009-04-16 | Evonik Degussa Gmbh | Process for the controlled hydrolysis and condensation of epoxy-functional organosilanes and their condensation with further organofunctional alkoxysilanes |
| DE102007040246A1 (en) * | 2007-08-25 | 2009-02-26 | Evonik Degussa Gmbh | Radiation-curable formulations |
| DE102007040802A1 (en) * | 2007-08-28 | 2009-03-05 | Evonik Degussa Gmbh | Composition containing low VOC aminoalkyl-functional silicon compounds for coating paper or film |
| DE102008007261A1 (en) * | 2007-08-28 | 2009-03-05 | Evonik Degussa Gmbh | Aqueous silane systems based on bis (trialkoxysilylalkyl) amines |
| DE102007045186A1 (en) * | 2007-09-21 | 2009-04-09 | Continental Teves Ag & Co. Ohg | Residue-free, layer-forming, aqueous sealing system for metallic silane-based surfaces |
| DE102007049743A1 (en) * | 2007-10-16 | 2009-04-23 | Evonik Degussa Gmbh | Silicon-titanium mixed oxide powder, dispersion thereof and titanium-containing zeolite produced therefrom |
-
2004
- 2004-07-01 DE DE102004031785A patent/DE102004031785A1/en not_active Withdrawn
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2005
- 2005-06-16 WO PCT/EP2005/006481 patent/WO2006002773A1/en not_active Ceased
- 2005-06-16 US US11/571,441 patent/US8911638B2/en active Active
- 2005-06-16 JP JP2007518491A patent/JP5090907B2/en not_active Expired - Fee Related
- 2005-06-16 PL PL05755290T patent/PL1761461T3/en unknown
- 2005-06-16 CN CN2005800224124A patent/CN1980861B/en not_active Expired - Lifetime
- 2005-06-16 EP EP05755290.3A patent/EP1761461B1/en not_active Expired - Lifetime
- 2005-06-16 ES ES05755290.3T patent/ES2672307T3/en not_active Expired - Lifetime
-
2010
- 2010-08-20 US US12/860,164 patent/US20100308287A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US8911638B2 (en) | 2014-12-16 |
| EP1761461B1 (en) | 2018-03-07 |
| CN1980861A (en) | 2007-06-13 |
| EP1761461A1 (en) | 2007-03-14 |
| DE102004031785A1 (en) | 2006-01-26 |
| CN1980861B (en) | 2012-08-29 |
| ES2672307T3 (en) | 2018-06-13 |
| US20100308287A1 (en) | 2010-12-09 |
| JP2008504204A (en) | 2008-02-14 |
| WO2006002773A1 (en) | 2006-01-12 |
| PL1761461T3 (en) | 2018-08-31 |
| US20090261309A1 (en) | 2009-10-22 |
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